Basic indazole azo compounds

ABSTRACT

BASIC DYES OF THE INDAZOLE SERIES OF THE FORMULA   (1,2-DI(A-),3-(K-N=N-),R3-1H-INDAZOLE)(+) X(-)   WHEREIN A IN METHYL, ETHYL OR A HYDROXYETHYL GROUP WHICH MAY BE FURTHER SUBSTITUTED WITH THE PRIVOSO THAT NOT MORE THAN ONE A IS METHYL OR ETHYL, R2 IS HYDROGEN, METHYL, METHOXY, CHLORO, NITRO, OR SO2R WHERE R IS AN AMINO RADICAL OR AN ALKYL OR ARYL RADICAL K IS A NITROGENEOUS COUPLING COMPONENT WHICH COMPLETES THE DYE MOLECULE ACID FORM A DIAZACYANINE SYSTEM AND X$ IS A COLORLESS ACID ANION. THE ORANGE TO BLUE DYES HAVE EXCELLENT FASTNESS PROPERTIES AND ARE SUITABLE FOR DYEING ANIONICALLY MODIFIED TEXTILE FIBERS, PARTICULARLY ACRYLONITRILE POLYMERS AND POLYESTERS.

United States Patent 3,826,800 BASIC INDAZOLE AZO COMPOUNDS JohannesDehnert and Guenter Dunkelmann, Ludwigshafen, Germany, assignors toBadische Anilin- & Soda- Fabrik Aktiengesellschaft, Ludwigshafen(Rhine), Germany No Drawing Filed Sept. 7, 1971, Ser. No. 178,384

Int. Cl. C09b 43/00 U.S. Cl. 260-147 4 Claims ABSTRACT OF THE DISCLOSUREBasic dyes of the indazole series of the formula The invention relatesto basic azo dyes having the formula (I):

Where A denotes methyl, ethyl or a radical having the formula --CHCHOH---R or ---CH ---CHOHR R denotes hydrogen, carbamoyl, N-substitutedcarbamoyl, carboxyl, hydroxymethyl, alkoxymethyl having two to sevencarbon atoms, phenoxymethyl or chloromethyl;

R independently of R denotes hydrogen, carbamoyl,

N-substituted carbamoyl, carboxyl, hydroxymethyl, alkoxy methyl havingtwo to seven carbon atoms, phenoxymethyl or chloromethyl;

R denotes hydrogen, methyl, methoxy, chloro, nitro or 80 R;

R denotes the radical of ammonia or an unsubstituted or substitutedaliphatic, araliphatic, cycloaliphatic, aromatic or saturatedheterocyclic amine or an unsubstituted or substituted alkyl or arylradical;

K denotes the radical of a nitrogen-containing isocyclic aromatic orheterocyclic aromatic coupling component which makes up the remainingpart of the molecule to a diazacyanine system,

X denotes the anion of an inorganic or organic acid and one of theradicals A does not denote methyl or ethyl.

3,826,800 Patented July 30, 1974 In addition to the meanings alreadygiven, R or R may for example denote the following radicals:N-methylcarbamoyl, N ethylcarbamoyl, N,N dimethylcarba-moyl,methoxymethyl, ethoxymethyl, butoxymethyl, fi-rnethoxyethoxymethyl, 5ethoxyethoxymethyl or ,B-butoxyetho'xymethyl.

When the radical SO R denotes a substituted sulfonamido group, theradical R may be derived from a primary or secondary amine which maybear other substituents. Examples of such substituents are aryl,aralkyl, alkyl, cycloalkyl, hydroxyl or alkoxy groups, dialkylamino ortetralkylammonium radicals, carboxylic acid, Carboxamido or nitrilogroups, acylamino groups, unsubstituted or substituted sulfonamidogroups, heterocyclic radicals and also halogen atoms.

Specific substituents for the amines, other than those already mentionedas being suitable, are phenyl, cyclohexyl, benzyl, phenylethyl, methyl,ethyl, methoxy, ethoxy, butoxy, phenoxy, dimethylamine, dibutylamino,tetramethylammonium, N,N dimethylcarbamoyl, N-methylcarbamoyl, N,Ndiethylcarbamoyl, N,N dimethylsulfonamido, N,N-diethylsulfonamido,N-phenylsulfonamido, acetylamino, propionylamino, chlorine or bromine.

The following are examples of primary and secondary amines: methylamine,dimethylamine, ethylamine, diethylamine, fi-hydroxyethylamine,propylamine, butylamine, methyl B hydroxyethylamine, 'ymethoxypropylamine, benzylamine, phenylethylamine, morpholine,piperidine, N-rnethylpiperazine, hexamethylenimine, thiomorpholinedioxide, 2,6-dimethylmorpholine, cyclohexylamine, pyrrolidine,piperazine, aniline, N-methylaniline, 4-su1fonamidoaniline, y (2ethylhexoxy) propylamine, 7-dimethylaminopropylamine andB-thiomorpholine, dioxide ethylamine.

When the R radical denotes a sulfonic group, R may for example have thefollowing meanings: methyl, ethyl, benzyl, B cyanoethyl, ,8carboxamidoethyl, ,B carboxyethyl, ,B-carbomethoxyethyl,,B-carboethoxyethyl, phenyl, methylphenyl, o-methylphenyl orp-chlorophenyl.

Compounds which together with the diazo component are capable of forminga diazacyanine system are used as coupling components K. Examples ofsuch coupling components are anilines capable of coupling in thep-position or aminonaphthalenes or heterocycles such as indoles orderivatives of benzothiazole, benzimidazole or trimethylindoline. Thecoupling components may contain further substituents such as halogenatoms, alkyl groups or alkoxy groups. The amino nitrogen atom of theanilines and aminonaphthalenes is preferably monosubstituted ordisubstituted.

The following are specific examples of coupling components:

N-methylaniline,

N-butylaniline,

dimethylaniline,

diethylaniline,

N,N-dibutylaniline, N,N-di-B-hydroxyethylaniline, N-methyl-N--hydroxyethylaniline, N-methyl-N-fl-cyanoethylaniline,N-ethyl-N-fi-hydroxyethylaniline, N-ethyl-NB-cyanoethylaniline,N-methyl-N- -methoxyethylaniline, N-methyl-N-fi-ethoxyethylaniline,N-ethyl-N-fl-rnethoxyethylaniline, N-ethyl-N-benzylaniline,N-ethyl-N-p-phenylethylaniline, N-fl-cyanoethyl-N-benzylaniline, N-8-hydroxyethyl-N-B-phenylethylaniline, N-cyclohexylaniline orN-cyclohexyl-N-B-hydroxyethylaniline,

and compounds bearing methyl, ethyl, methoxy, ethoxy,

chlorine, acetylamino or propionylamino as substituents in the orthoand/ or meta positions to the amino group.

The following are also suitable:

N-methyl-4-ethoxydiphenylamine, 4-acety1aminodiphenylamine,N-phenylpyrrolidine,

N-phenylmorpholine, N-phenylthiomorpholine dioxide,l-phenyl-3,3,S-trimethylpyrazoline, tetrahydroquinaldine,Z-methyldihydroindole,

indole,

2-.methylindole, l-cyanoethyl-Z-methylindole, 2-phenylindole,

1-methyl-2-phenylindole, 1-cyanoethyl-2-phenylindole,2-phenylindole-l-propionic acid, Z-phenylindole-l-propionamide,2-cyanomethylbenzimidazole, 1,3-dimethyl-2cyanomethylenebenzimidazoline,1,3,3-trirnethyl-2-cyanomethyleneindolenine,1-methyl-4-cyanomethylenedihydropyridine, 2-benzimidazolylacetamide,di-2-benzimidazolylmethane and di-Z-benzothiazolylmethane.

Examples of aminonaphthalenes are: l-naphthylamine, 1ethylaminonaphthalene, l methylaminonaphthalene, 1dimethylaminonaphthalene, 1 diethylaminonaphthalene, 1cyclohexylaminonaphthalene, 1 benzylaminonaphthalene, 1phenylaminonaphthalene, 1 p tolylaminonaphthalene, 1 (pethoxyphenylamino) naphthalene, 1 (p ,8 hydroxyethoxyphenylamino)naphthalene, 1 ,(p methoxyphenylamino) naphthalene, l- (pacetaminophenylamino) naphthalene and 1(phydroxyphenylamino)-naphthalene.

The benzene ring of the diazo component may contain, in addition to the80 R group, other substituents such as methyl, methoxy, ethyl, ethoxy,acetylamino, benzoylamino, chlorine or bromine.

It is prefered however to use diazo components which do not contain anyof these additional substituents.

Examples of suitable anions are chloride, bromide, nitrate, sulfate,methosulfate, ethosulfate, benzenesulfonate, toluenesulfonate, citrate,formate, acetate, tetrachlorozincate or tetrafiuoroborate.

The new dyes are blue, violet, red, orange or yellow depending on thecoupling component chosen. Since the fastness properties of the new dyesare substantially unaffected by the type of substituents in the sulfonicand sulfonamido groups, all radicals of primary or secondary amines aresuitable as substituents for the sulfonamido groups. The amine chosenthus depends mainly on practical considerations, particularly on theeflfect which the 80 R substituent is to exert on the aflinity and therate of absorption of the dye.

Dyes having the formula (I) may be prepared for example by reacting acompound having the formula (II):

in which R and K have the meanings given above with a compound havingthe formula (III):

in which R and R have the meanings given above.

In the case when one of he radicals A denotes methyl or ethyl, thecompounds having the formula (II) may first be monoalkylated for examplewith dimethyl sulfate or diethyl sulfate and the reaction products maybe reacted with the compounds having the formula (III). The reversesequence of alkylation is also possible and in some cases preferred.

Examples of compounds having the formula (III) are: ethylene oxide,1,2-propylene oxide, epichlorohydrin, glycidamide, glycidyl ethyl ether,glycidyl phenyl ether or glycidyl alcohol.

Reaction of compounds having the formula (II) with compounds having theformula (III) is preferably carried out in acid medium, advantageouslyin the presence of an organic acid, for example formic acid, aceticacid, propionic acid, benzoic acid or p-toluene-sulfonic acid, butinorganic acids such as sulfuric acid, phosphoric acid or hydrogenhalides may be used. These acids may be used in the concentratedcommercial form, as dilute solutions in water or mixed with organicsolvents with or without water.

When the reaction is carried out in the presence of organic acids theconcentrated form of these acids is usually employed, if desiredtogether with organic solvents. Suitable solvents are hydrocarbons suchas benzene, toluene or xylene, halogenated aliphatic or aromatichydrocarbons such as chloroform, ethylene chloride, chlorobenzene ordichlorobenzene, alcohols such as ethanol, ethylene glycol or benzylalcohol, ketones such as acetone or cyclohexanone, esters such as ethylacetate, ethers such as ethylene glycol dimethyl ether or dioxane. Thereaction may also be carried out in the presence of ptoluenesulfonicacid, boron trifiuoride or zinc chloride.

The reaction is advantageously carried out at temperatures of from 0 to180 0., preferably at 30 to C. The compounds having the formula (II) arepreferably Wholly or partly dissolved in the acid-containing mixture forthe reaction and then a compound having the formula (III) is addedeither all at once or gradually.

Those of the new dyes are generaly preferred which have the generalformula (Ia) or (lb):

in which R X and K have the meanings given above.

A group of blue dyes having particular industrial importance has thegeneral formula:

in which A denotes methyl or ,B-hydroxyethyl;

R denotes ethyl, cyclohexyl, p-methylphenyl, p-hydroxyethoxyphenyl,p-hydroxyphenyl, p-methoxyphenyl or p-ethoxyphenyl,

one of the radicals A not being methyl, and

R and X- have the meaning given for formula (Ia).

Particularly valuable violet to blue dyes have the general formula:

B denotes hydrogen, methyl or acetylamino;

R denotes hydrogen, methyl, ethyl, butyl, B-hydroxyethyl, fl-cyanoethyl,cyclohexyl, benzyl, phenylethyl, phenyl, p-methoxyphenyl orp-ethoxyphenyl; and

R denotes methyl, ethyl, butyl or fi-hydroxyethyl, one

- of the radicals A being other than methyl; and

R and X- have the meanings given above.

Preferred radicals R are hydrogen, chlorine, nitro and 50 R, thesulfonamides being preferred to the sulfones.

Preferred radicals R are derived from monoalkylamines or dialkylamineshaving one to eight carbon atoms in all, and the alkyl radicals may bearhydroxy, methoxy, ethoxy or fl-hydroxyethoxy as substituents.Cyclohexylamine, aniline, pyrrolidine, piperidine, morpholine, N-methylpiperazine or thiomorpholine-S-dioxide are also suitable.

Specific examples of the first group are methylamine, ethylamine,propylamine, butylamine, dimethylamine, diethylamine, dibutylamine, Bhydroxyethylamine, p hydroxypropylamine, 'y-hydroxypropylamine, Nmethyl-N- fl-hydroxyethylamine, N-ethyl-N-p-hydroxyethylamine, N-methyl-N-p-methoxyethylamine, N-(fi-hydroxy)-ethoxy ethylamine,fl-methoxyethylamine, -methoxypropylarnine or -ethoxypropylamine.

Particularly valuable orange or red dyes correspond to the generalformula:

in which R and X have the meanings given for formula (Ia) and R denotesa hydrogen atom, a methyl group or the radical of a propionic acid,amide or nitrile attached in the ,8-position and R denotes a methyl orphenyl group.

The new dye salts are basic dyes which have more or less good solubilityin water depending on the type of substitution, the size of the wholemolecule and the type of anion. The solubility in water can becontrolled to a certain extent by exchanging the anion, for example bypreparing the free base from the fairly sparingly soluble dye chlorideor methosulfate by means of alkali and then dissolving the free base inan acid whose anion makes the dye better soluble in water. Examples ofsuch acids are nitric acid, formic acid, citric acid, acetic acid andtrichloroaoetic acid. Conversely the dye salt may be converted into asalt which is sparingly soluble or wholly insoluble in water, forexample by introducing into the dye an anion such as tetrafluoroborateor potassium hexacyanoferrate (II) or an anion derived from aheteropolyacid or a dye containing a sulfonic acid group. New dyeshaving hydroxyalkyl groups generally have better solubility in waterthan comparable dyes having alkyl groups.

The soluble new dyes may be used in the form in which they are obtainedby the synthesis or in a finished or dispersed form for dyeing textilematerial such as mordanted cotton, leather and materials such as fibers,flock, filaments threads, sheeting, film, spun goods, woven and knittedcloth of synthetic materials such as cellulose esters, cellulose ethers,polyamides or polyesters, especially when these have been modified byincorporation of anionic groups. They are particularly suitable fordyeing polyacrylonitrile and copolymers of acrylonitrile and alsoanionically modified polyesters, very fast dyeings being obtained.

The following Examples illustrate the invention. Parts and percentagesrelate to weight unless otherwise stated.

EXAMPLE 1 A slow stream of ethylene oxide is passed for several hours at60 C. into a solution of 21 parts of the compound having the formula:

in 200 parts of glacial acetic acid until complete alkylation to theblue dye has taken place as shown by thin layer chromatography. Thereaction mixture is then introduced into 2000 parts of water and theproduct having the (LEE-CH2 O H is precipitated by adding 350 parts byvolume of sodium chloride solution, isolated and dried. A dark bluepowder is thus obtained which dissolves readily in water and dyesacrylonitrile polymers outstandingly fast blue shades.

EXAMPLE 2 45 parts of epichlorohydrin is added to 20.5 parts of thecoupling product of 3-aminoindazole and p-ethoxyphenylu-naphthylamine in200 parts of glacial acetic acid and the whole is heated to 60 C.Another 45 parts of epichlorohydrin is added over twelve hours in orderto complete the reaction. After it has been established by thin layerchromatography that quantitative reaction to the quaternary dye:

Cl-CHz-CH-CHz-N as N N OH \N/ NH-Q-O 02m 01 has taken place, thereaction mixture is allowed to flow into 3000 parts of water and theproduct is precipitated with parts of saturated salt solution. The driedand ground dye dyes acrylonitrile polymers fast blue shades.

7 EXAMPLE 3 26 parts of the coupling product having the formula:

in 200 parts of glacial acetic acid is reacted with ethylene oxide at 60C. and the quaternary dye crystallizes out from the reaction mixture.The dye powder obtained after isolation and drying dissolves well in hotwater and gives outstandingly fast blue shades on acrylonitrilepolymers.

EXAMPLE 4 75 parts of phenyl glycidyl ether is added to a solution of 20parts of the compound:

in 200 parts of glacial acetic acid and the whole is heated at 60 C.until according to a thin layer chromatogram a complete reaction hastaken place. 25 parts of zinc chloride is then added to the reactionmixture, the whole is introduced into 1000 parts of ice-water and thedeposited dye is isolated in the usual way. It dyes acrylonitrilepolymers fast violet shades.

EXAMPLE 5 EXAMPLE 6 11 parts of the coupling product having the formula:

is quaternized in 100 parts of glacial acetic acid with ethylene oxideat 60 C. After the reaction is completed, the reaction mixture has 80parts of zinc chloride in 250 parts of water added to it, thequaternization product is precipitated with 1200 parts by volume ofsaturated sodium chloride solution, suction filtered, washed with waterand dried. The brown dye gives bright yellow shades when dyed ontoacrylonitrile polymers.

EXAMPLE 7 40 parts of the compound having the formula:

t-N a) 2 tion mixture is introduced into a mixture of 3000 parts of zincchloride and 200 parts of water. The dye is isolated and dried as usualand gives an outstandingly fast violet dyeing on acrylonitrile polymers.

EXAMPLE 8 14.5 parts of the compound obtained according to the firstparagraph of Example 7 is quaternized in 200 parts by volume ofchloroform with 37.8 parts of dimethyl sulfate with an addition of 3parts of sodium carbonate at the boiling point. When the reaction isover the chloroform is evaporated and the residue is dissolved in 200parts of 30% acetic acid. The dye is precipitated by adding 500 parts byvolume of saturated sodium chloride solution, suction filtered, washedwith water and dried. Violet dyeings having good fastness properties areobtained therewith on acrylonitrile polymers.

EXAMPLE 9 20.5 parts of the azo compound having the formula:

is methylated in 200 parts by volume of dioxane with 26 parts ofdimethyl sulfate and 5 parts of magnesium oxide at 60 C. untilchromatographic examination indicates that the starting compound hasreacted completely. The reaction mixture is then introduced into 2000parts of water and the precipitate is suction filtered and washed withwater to remove quaternary permethylated dye. The monomethyl compoundwhich remains is quaternized in the usual way in 200 parts by volume ofglacial acetic acid with ethylene oxide at 60 C. After the reaction isover, the mixture is introduced into 2000 parts of water and the dye isisolated after it has been precipitated with sodium formate. A dark bluepowder is obtained which dyes acrylonitrile polymers fast blue shades.

EXAMPLE 10 20.7 parts of the compound having the formula:

dissolved in 200 parts of glacial acetic acid is quaternized at 60 C.with 13 parts of dimethyl sulfate and by passing in ethylene oxide atthe same time. After the reaction is over, the reaction mixture isdiluted with 2000 parts of Water and the dye mixture is precipitatedwith 200 parts by volume of sodium chloride solution and isolated. Thedark blue powder obtained dyes acrylonitrile polymer fast blue shades.

Dyes characterized in the following Table by specifying theirsubstituents may be obtained by methods analogous to those described inthe Examples:

All the dyes in the Table give blue dyeings on acrylonitrile polymers:

TABLE-Continued Ex. I R R R Epoxlde ea H H H Ethylene oxide.

- S Or-NH- 64 -S0r-CHzCH|CO0H H H Same as above Do.

65 H H H Do. xx .1 I I G H Cl H Same as above. Do. H H do.'. Do.

H H .....de D0.

69 H H H .de Eplchlorohydrin. 70 H H H 1,2-propy1ene oxide H H Hlycidamlde. 72 H Cl H D0. 73 H 01 H d0 Epichlorohydrin.

74 11 H H v Ethylene oxide.

75......- H H H De. 0CHa 76 H H E Q Do.

NII,

77 H H H Do.

--NH- O O C H:

H H Same as above Eplchlorohydrln.

H H -do Glycldamlde.

H H .do 1,2-propylene oxlde.

H C H; C H; Ethylene oxide.

H CH; C H: 1,2-propy1ene oxide.

H CH; CH; Eplchlorohydrln.

H CH: CH: Glycldamide.

H CH; CH; Glycidyl ethyl ether.

Cl CH; CH; Ethylene oxide.

01 CH; CH; Eplchlorohydrln.

H CH; CH; Ethylene oxide.

H CH; CH; Do.

H H (12H! D0:

H H 02H: Glycidyl phenyl ether.

H H C1115 Eplchlorohydrln.

C! H 01H Ethylene oxide C] H 01H; Epichlorohydrln.

H H 02H; Ethylene oxide.

L N ?NN NH\ /C H: CH Hz a H Ex. R R Epoxide Shade 96. H H Ethylene Blue.

oxide. 97.-.. H Cl .-...do D0.

98. H .-....do Do. S Oz-NH 99. H Cl Eplchloro- Do.

hydfln. 100. H H Glycidamlde... Do. 101. H H Glycidyl Do.

alcohol.

1 7 EXAMPLE 168 21 parts of the coupling product having the formula isreacted with ethylene oxide in 200 parts by volume of chlorobenzeneafter the addition of 1 part of p-toluenesulfonic acid and at to C.untilthe starting compound, according to thin layer chromatographicinvestigation, has been almost completely converted into themonoalkylated dye. Introduction of ethylene oxide is then interruptedand 6.3 parts of dimethyl sulfate is added to the reaction mixture whichis then stirred for another ten hours at 60 to 70 C. The quaternary dyesalt is filtered 01f to isolate it. It produces outstandingly fast blueshades on acrylonitrile polymers.

Dyes which are characterized in the following Table by reference totheir substi'tuents and the expoxide used for the alkylation may beobtained by methods analogous to those described in the Examples.

' i f HN c-N=N--N-n Ex. R R R R R Epoxide Shade 169...- N0: 11 CaHs 01H;H Glycldyl alcohoL- Blue. N0, H C Hi 01H! CH; Ethylene oxide-. Do.171..-- N0; H 01H; --CHzCHr-OH CH; -.-..do Do.

172...- NO H C H CH: ..-..do Do.

173.... N0 H CzHr H -....do Bluish violet. -CH:-

174...- N01 H -CH OH-.- OH CH;CHOH CHa --.d0 Blue.

175-... N0; H CHz-CH:0H NH-COCH; .....d0 Do.

176.... N0 H H CH: .....do Do.

177."- NO| H H '(CH2)s--CH 178.--. NO: H (CHz)r-CH1 (CHz) -:CH3 179...-NO: H H Q N=N N U Ex. R R B. R Epoxide Shade C H H H Ethyleneoxlde..-...-- Blue.

S OzNH-(CH:)|N

I CgH 1 -S O NH- OH OH Y H H '.....(10 Do; 18 2- a): I a i SO NH-(CH)0-(CH) OH H Sameasabove.. (10 -SO: NH-(CH:):0CH; 2 H H do I (in H H do(in Do, -SO:|'N S09 H B do do Do.

--S Og-N N-CHI me 01 I H n M 4 an 100.

187 02H: H H ---.-d0 D0.

l v, I v I TA"BLEContinued V n I: V v Ex. 1 R m I R? R E'indilde "shade188 0,113 H H Ethylene oxide Blue -s OFNH- oHm-N l a I? v x 189 CH2):-0H I H v H H H Sameasabove... cln D '-sor-N (CHM-0H -SOz-NH(CH2)OH' H Hno. S Or-NH-(CHzh-O-(OHflrOH H H D0. -S Oz-NH--(CH2)2OCH3 H H Do.

H H Do. S 03-N N-CHa 194 Cl H H Do.

195 H H D0.

-S Or-NH- 196 01 H H Sameasabove do Do. 197 H 01 H ..d0 d0 Do.

H 01 H '..do.-.. Do. 198 NH 0o-om V 199 H H Same as above do Do.

-S 02-NH- 2 H H H .....do.... Do.

00 --o-om-cm-on H H H Same as above. 1,2-pr0pylene oxide Do. H H H..-..do Eplehlorohydrim. Do. H 01 H d0 Ethylene 0x lde Do. Cl H H do doDo. NO: H H --.--d0 d0 D0 S OzNH-(CH1)3'OCH3 H H .--..d0 ..'.do Do H Hrln Do. -S (Dz-Nd S 02-NH- We'claim: 1. A basic azo dye of the indazoleseries having the 4f formula:

in which:

A is methyl or ethyl or the radical of the formula CH;;r-CH0HR with theproviso that not more than one A is ethyl or methyl;

R is hydrogen, carbamoyl, carboxyl, hydroxymethyl 60 alkoxymethyl havingtwo to seven carbon atoms, phenoxymethyl or chloromethyl; R is hydrogen,methyl, methoxy, chloro, nitro or SO R;

R is methyl; S-cyanoethyl; B-carbamoylethyl; fl-carboxyethyl; alkylaminoof one to eight carbon atoms 65 4 K is a coupling comp'o'nent'of theformula R is ethyl, cyclohexyl, p-methylphenyl, fl-hydroxyethoxyphenyl,p-hydroxyphe'nyl, p-methoxyphenyl or p-ethoxyphenyl;

B is hydrogen, methyl or acety lamino;

vR is hydrogen, methyl, ethyl, butyl, B-hydroxyethyl, fl-cyanoethyl,cyclohexyl, benzyl, phenylethyl, phenyl, p-methoxyphenyl orp-ethoxyphenyl;

R is methyl, ethyl, butyl or fl-hydroxyethyl;

R" is hydrogen, methyl fi-carboxyethyl, fl-carbomoylethyl orfi-cyanoethyl; and

R is methyl or phenyl; and X is the anion of an inorganic or organicacid.

2. A dye as claimed in Claim 1 having the formula where R and X have themeanings given in Claim 1; R is hydrogen, methyl, fl-carboxyethyl,fi-carbamoylethyl or fl-cyanoethyl; and R is methyl or phenyl.

3. A dye as claimed in Claim 1 and having the formula:

where A denotes methyl or fi-hydroxyethyl; R denotes ethyl, cyclohexyl,p-methylphenyl, fi-hydroxyethoxyphenyl, p-hydroxyphenyl, p-methoxyphenylor v p-ethoxyphenyl;

22 one of the radicals A denoting other than methyl; and R and X havingthe meanings given in Claim 1.

4. A dye as claimed in Claim 1 and having the formula:

:32 Q Xe A -N GN=N N-Rs \e/ I in N B l,

where References Cited UNITED STATES PATENTS 3,697,501 10/ 1972 Dehnert26016.3 3,726,852 4/1973 Calla et al 260-462 LORRAINE A. WEINBERGER,Primary Examiner C. F. WARREN, Assistant Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE @ETTFTCATE 0F QURRECTIO PATENT NO. I 3, 826,800 DATED July 30, 1974 'NVENTOR(5) 3 Johannes Dehnert et al.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

In Column 1, after line 6, insert "Claims priority, application Germany,September 10, 1970, P 20 44 823.1"

In Column 1, Line 58, delete "alkoxy methyl" and Q substitute-alkoxymethyl- In Column 6, the formula under Example 2, the rightbracket should be inserted in front of the chlorine anion so as toexclude the chlorine anion.

In Column 8, Line 9, insert after "parts" -by volume of a. saturatedsolution of sodium chloride, 134 parts-- In Column 16, Example 155,under the column "R of the II II a table, delete C H and substitute C HIn Column 20, Claim 1,. in the third formula,

7 7 delete N and substitute R I /N D Bigned and Scaled this Qtwenty-second Day Of June 1976 [SEAL] Attest:

RUTH C. MASON c. MARSHALL DANN 14' 8 11 ('mnmissimru ojlarnts andTrademarks

